JPH09132722A - Thermoplastic resin composition and molding using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition useful for molding having a small kinematic friction coefficient, excellent in slipping property and superior in blocking resistance and transparency by homogeneously dispersing a specific amount of fine grains of globular silicone resin having a specific group bound to its surface into a thermoplastic resin. SOLUTION: This resin composition is obtained by homogeneously dispersing (B) 0.1-10 pts.wt. of fine grains of globular silicon resin of 5.0-20μm average diameter having a polysiloxanyl group of formula I [R is a 1-12C (non) substituted hydrocarbon, in which more than 50mol% in the R is methyl; (n) is an integer of more than 5 and less than 200] bound to the surface into (A) 100 pts.wt. of a thermoplastic resin. The component B is preferable to be the hydrosilylation product of fine grains of globular silicon resin comprising the formula CH2 =CHSiO1.5 unit with the compound of formula II. The components are preferably blended in the ratio of 0.1-10 pts.wt. preferably 0.2-5 pts.wt. component B per 100 pts.wt. component A.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic resin which gives a molded article having a small dynamic friction coefficient, good sliding property, excellent blocking resistance, good water repellency and stain resistance, and excellent transparency. The present invention relates to a resin composition and a molded article using the resin composition.

[0002]

2. Description of the Related Art Polystyrene, polymethylmethacrylate, polypropylene, polyethylene, polyvinyl chloride,
Polyacetal, polyurethane, polyester, AB
Thermoplastic resins such as S and AS are used in large quantities as general-purpose resins because they are excellent in moldability, processability, transparency, easy coloring, etc. and inexpensive, and are processed into various molded products such as films and sheets. Has been done. However, when processed into a film or sheet, especially soft resins such as polyethylene, polyvinyl chloride, and polypropylene tend to block easily,
It has been pointed out that stickiness between the sheets is generated in addition to making a strange noise such as crunching when rewinding the rolled-up material. Further, in the case of a hard resin molded product such as polystyrene or polyacetal, the mold releasability from the mold is poor, and improvement in processability has been demanded. Further, since these resin molded products have poor slip, it has been necessary to improve the slidability in terms of productivity and feeling of the molded products themselves.

As a countermeasure, silicone oil, which is a lubricant and a mold release agent having excellent chemical and physical stability, was added to the thermoplastic resin. However, the silicone oil near the surface layer of the molded product was added. Since most of them exude and are consumed in a short period of time, they exhibit excellent slipperiness at the initial stage, but are insufficient in terms of long-term maintenance of sliding characteristics. In addition, there is also a problem that the surface of the molded article is sticky, and the commercial value is reduced.

As a method for solving these problems, a method of kneading a true spherical silicone powder (see, for example, Japanese Patent Laid-Open No.
1-168408, JP-A 1-204950, JP-B 7-39214), a method of kneading silicone rubber and polytetrafluoroethylene powder (refer to JP-A-4-234450), silicone oil and polyflour. A method of kneading vinylidene chloride powder (see Japanese Patent Laid-Open No. 4-264152) and a UV-curable resin containing spherical silica fine particles (Japanese Patent Laid-Open No. 7-1021).
Japanese Patent Publication No. 86) is proposed. This method of mixing powder and spherical fine particles is effective, but also has unsatisfactory properties. The content of powder and the like is relatively large at 2% by weight or more, which is unsuitable for molded products such as films requiring transparency. It is also economically disadvantageous. Further, the solid lubricant has a drawback that the slidability is gradually deteriorated due to abrasion powder due to abrasion.

Further, a method in which an acrylic resin (graft copolymer) obtained by copolymerizing a silicone macromonomer is kneaded with a thermoplastic resin to obtain a film or other molded article having slipperiness (Japanese Patent Laid-Open No. 1-214475, JP-A-4-173869 and JP-A-6-100746 are also proposed), but they have good dispersibility because they are well compatible with vinyl resins, and as a result, the characteristics are insufficient with a small amount of compounding. However, since the silicone-grafted acrylic resin itself is an irregularly shaped powder, there is a drawback that friction is likely to occur on the surface layer.

[0006]

DISCLOSURE OF THE INVENTION The present invention is a thermoplastic resin composition which does not have the above-mentioned problems, has a small dynamic friction coefficient, has a good slip property, is excellent in blocking resistance, and gives a molded article having good transparency. The present invention is intended to provide a product and a molded product using the product.

[0007]

Means for Solving the Problems The present inventors have reached the present invention as a result of paying attention to a method of adding spherical fine particles and making intensive studies on its improvement. The thermoplastic resin composition of the present invention solves the above-mentioned problems. It is obtained by adding 100 parts by weight of a thermoplastic resin to the surface of the general formula (I).

Embedded image (In the formula, R represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, 50 mol% or more of all R are methyl groups, and n represents an integer of 5 or more and 200 or less. ), The average particle size of the polysiloxanyl group bonded is 0.5 to 20 μm.
0.1 to 10 parts by weight of the spherical silicone resin fine particles are uniformly dispersed. A molded article produced from this thermoplastic resin composition solves the above-mentioned problems.

Hereinafter, the present invention will be described in detail. The thermoplastic resin used in the present invention is a resin such as polyethylene, polypropylene, polystyrene, polymethylmethacrylate, AS resin, ABS resin, polyvinyl chloride, polyacetal, polyurethane or polyester.
There is no particular limitation as long as it is a thermoplastic resin.

The spherical resin fine particles dispersed in the thermoplastic resin are spherical silicone resin fine particles having the polysiloxanyl group represented by the general formula (I) bonded to the surface thereof. The target characteristics are obtained when the average particle size of the resin fine particles is in the range of 0.5 to 20 μm. It is considered that when the average particle diameter is less than 0.5 μm, it becomes difficult for the resin fine particles to protrude from the surface of the molded product in the case of forming a molded product such as a film or sheet, but the slip property becomes insufficient. On the other hand, if the average particle size exceeds 20 μm, the transparency is significantly impaired when formed into a film, which is not preferable. The amount of the resin fine particles to be blended is 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the thermoplastic resin. With this blending amount, slipperiness, blocking resistance, slidability, etc. are improved. If the amount of fine resin particles blended is less than 0.1 parts by weight, slip properties cannot be obtained, and if it is blended in excess of 10 parts by weight, sliding properties become uncertain and the dynamic friction coefficient does not decrease, which is economically disadvantageous. .

A suitable method for binding the polysiloxanyl group to the surface of the silicone resin fine particles is a hydrosilylation reaction or a silylation reaction (deammonification reaction) between a silanol group and a compound having a silicon-nitrogen bond.
Can be used. For the hydrosilylation reaction, the general formula (II)

Embedded image The compound shown by is mentioned as one raw material. Further, in the deammonification reaction, the general formula (III)

[Chemical 6] The compound shown by is mentioned as one raw material. R in both formulas represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, 50 mol% or more of all R are methyl groups, and n represents an integer of 5 or more and 200 or less. It is a thing. The compound represented by the general formula (II) or the general formula (III) can be produced by a known method.

In order to utilize the hydrosilylation reaction, for example, first, CH ₂ = CHSiO _1.5 units are introduced to prepare silicone resin fine particles having vinyl groups on the particle surface, and then,
The compound represented by the general formula (II) is hydrosilylated. The silicone resin fine particles having a vinyl group on the particle surface in the preceding stage are, for example, vinyltrimethoxysilane or vinyltriethoxysilane alone or a mixture with methyltrialkoxysilane dispersed in water in a finely divided state to form a basic or acidic catalyst. It is obtained by hydrolyzing below to form crosslinked fine particles, evaporating water, drying and pulverizing. The content of CH ₂ = CHSiO _1.5 unit is 5 mol% or more, preferably 10 mol% in the siloxane unit.
With the above, a sufficient amount of vinyl groups on the particle surface can be obtained. Then, the obtained silicone resin fine particles having a vinyl group on the particle surface are dispersed in an inert solvent, and the compound represented by the general formula (II) is subjected to hydrosilylation reaction in the presence of a catalyst. The conditions for the hydrolysis or hydrosilylation reaction may be set according to a conventional method including adjusting the particle size.

To utilize the deammonification reaction, for example, first, one or more of methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, etc. is used, and a silicone resin having a vinyl group on the particle surface is used. Hydrolysis is carried out in the same manner as in the case of the fine particles to form silicone resin fine particles having silanol groups on the surface of the particles, and then reacted with the compound represented by the general formula (III). Silanol group content is 0.00001-0.03mol /
It should be 100g. General formula when less than 0.00001 mol / 100g
Since the amount of the compound represented by (III) bound is small, slipperiness cannot be expected. On the other hand, if it exceeds 0.03 mol / 100 g, the particle size becomes too large during hydrolysis (adhesion is large) and the average particle size becomes 0.5.
It is difficult to obtain primary particles of -20 μm. The conditions of the hydrolysis or deammonification reaction may be in accordance with a conventional method. In the above method, silane or a mixture thereof is finely dispersed in water to carry out hydrolysis. By doing so, spherical resin fine particles are obtained, and this is excellent in a property imparting effect. Further, it is particularly preferable that the surface of the fine spherical resin particles is covered with a dimethylpolysiloxane chain.

R in the above general formulas (I) to (III) represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms. This includes alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, phenyl group, tolyl group,
Aryl group such as naphthyl group, alkenyl group such as vinyl group and allyl group, aralkyl group such as α-phenethyl group and benzyl group, and substituted alkyl group such as 3-chloropropyl group and 3,3,3-trifluoropropyl group Are exemplified, but industrially, a methyl group, an n-butyl group, and a phenyl group are preferable, and from the aspect of imparting properties such as slipperiness and blocking resistance,
At least 50 mol% of all R are methyl groups. n is an integer of 5 or more and 200 or less, and the required characteristics can be obtained in this range, but if it is less than 5, slipperiness is difficult to be expressed, and 2
If it exceeds 00, the resin fine particles become soft, which is disadvantageous in terms of blocking resistance.

Specific examples of the compound represented by the general formula (II) or (III) include the followings, but the invention is not limited thereto.

Embedded image

The spherical silicone resin fine particles having the polysiloxanyl group bonded to the surface obtained as described above are
Since primary particles having an average particle size of 0.5 to 20 μm are aggregated to form secondary particles, spherical particles having this particle size can be obtained by disintegrating with a crusher such as a jet mill, a hammer mill or a ball mill. Obtained as. As mentioned above, this powder is 0.1% based on 100 parts by weight of the thermoplastic resin.
˜10 parts by weight, preferably 0.2 to 5 parts by weight, and uniformly dispersed. A known device can be used for uniform dispersion, and the thermoplastic resin may be kneaded with the powder in a state of being melted by heating. As a result, the thermoplastic resin composition of the present invention is obtained. That is, each component is uniformly mixed with a blending machine such as a Henschel mixer, a ribbon blender, and a high-speed mixer in a predetermined ratio, and further, a uniaxial extruder,
A kneading machine such as a twin-screw extruder, a Banbury mixer, a pressure kneader, a co-kneader, and a mixing roll can be used to uniformly knead and disperse.

For the purpose of further improving the slidability, it is preferable to use spherical silicone resin fine particles having the polysiloxanyl group bonded to the surface thereof, which is impregnated with a liquid lubricant such as silicone oil or fluorine oil. Further, a solid lubricant such as polytetrafluoroethylene, polyvinylidene fluoride, or graphite can be added to the composition as long as other characteristics are not deteriorated. Further, as various auxiliary materials, a plasticizer, a light stabilizer, an antioxidant, a filler, a colorant, a processability improving agent, an antistatic agent, an ultraviolet absorber, a pigment, etc. may be added within a range that does not interfere with the purpose. it can.

The thermoplastic resin composition of the present invention obtained as described above can be molded into a desired form using a conventional extrusion molding machine, injection molding machine, calender molding machine or the like. A T-die / sheet feeder, a roll sheet feeder or the like can be used to form a film or sheet, but the molding method is not particularly limited. Molded products such as the obtained film and sheet have a small dynamic friction coefficient and good slipperiness,
It has excellent blocking resistance, water repellency, and stain resistance. Furthermore, impact resistance is also improved. This characteristic is due to the fact that the surface of the kneaded and dispersed spherical silicone resin fine particles is covered with the polysiloxanyl group bonded thereto, and particularly when the dimethylpolysiloxanyl group is excellent, excellent characteristics can be obtained. Moreover, while the conventional product having such characteristics has poor transparency, the thermoplastic resin composition of the present invention gives a molded product having good transparency. This thermoplastic resin composition of the present invention makes full use of its characteristics, and is used as various film-like packaging materials, medical product containers, cosmetic containers, food containers or other various containers, electric parts, machine parts, household products (for example, cups). , Plates), agricultural and marine products, building materials, miscellaneous goods, toys (for example, plastic models), and the like.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION Next, embodiments of the present invention will be described with examples. In addition, the part in an example represents a weight part.

[0019]

[Examples] Examples 1 to 3 and Comparative Examples 1 to 3 Polyvinyl chloride [TK-1300, trade name of Shin-Etsu Chemical Co., Ltd.] 35 parts, plasticizer (diisononyl phthalate) 35 parts, epoxidized large amount Soybean oil 3 parts, Ba-Zn stabilizer 3
Parts, 2 parts of polymethylmethacrylate (gelling accelerator) and various resin fine particles or silicone oil shown in Table 1 are mixed and kneaded on a 3.5 inch test roll (two rolls) at 150 ° C. for 10 minutes, A sheet was prepared by a roll sheet making machine. Then, this was sandwiched between mirror surface plates and preheated at 170 ° C. for 4 minutes, and then pressed at a pressure of 100 kgf / cm ² for 4 minutes to prepare a 120 × 120 × 1.0 mm test sheet. The appearance of the sample thus obtained, the dynamic friction coefficient,
The contact angle of water, the slip properties of the samples, and the stain resistance were measured, and the results are shown in Table 1.

The characteristics were measured by the following methods.・ Dynamic friction coefficient ・ ・ ・ ・ Measured using Kyowa Interface Science Co., Ltd. dynamic friction coefficient measuring device under the conditions of SUS ball with a load of 50 g and speed of 24 cm / sec.・ Water contact angle ・ ・ ・ ・ Contact Angl made by Kyowa Interface Science Co., Ltd.
It measured using e Meter.・ Slidability ・ ・ Stack the test sheets and roll a 500g iron roll on the sheets so that air does not enter between the sheets. After contacting the entire surface, place the upper sheet and the lower sheet on a flat surface. Slide in the direction of ° to check the degree of blocking.・ Stain resistance: ・ A contaminated material obtained by crushing and kneading a mixture of 30 parts of mulch, 5 parts of cement, 1 part of carbon black and 5 parts of mineral oil in a ball mill and uniformly adhering 1 g to 100 g of washed and dried sand. Then, the test sheet cut into 5 cm × 5 cm was contacted with stirring for 60 minutes at room temperature. Then, the degree of contamination on the surface of the test sheet is visually observed. ◎ ... No stain, ○ ... Almost no stain, × ... Stain on the entire surface

[0021]

[Table 1]

The resin fine particles in Table 1 are as follows.・ Resin particles 10 parts of spherical vinyl silsesquioxane powder with an average particle size of 2.0 μm, toluene 50 parts, average composition formula

Embedded image Organohydrogenpolysiloxane 1 represented by
Parts, 0.005 parts of a 2 wt% ethanol solution of chloroplatinic acid, and reacted at 120 ° C. for 6 hours, and toluene was distilled off under reduced pressure.
Further, after washing with hexane, the powder was separated by a centrifuge and dried at 80 ° C. for 2 hours to obtain resin fine particles whose surface was covered with a polydimethylsiloxanyl group. Resin fine particles KMP-590 [trade name of Shin-Etsu Chemical Co., Ltd.], methylsilsesquioxane powder with an average particle size of 1.5 μm.

Examples 4 to 6 and Comparative Example 4 100 parts of polyvinyl chloride, 35 parts of a plasticizer, 3 parts of epoxidized soybean oil, 3 parts of a Ba-Zn stabilizer and 2 parts of polymethylmethacrylate were used as polypropylene [Mitsui Petrochemical. Brand name Hypol J-600 manufactured by Co., Ltd.] 170 parts were prepared in the same manner as in Examples 1 to 3 except that various resin fine particles shown in Table 2 were added instead of 100 parts.
After kneading for 10 minutes at ℃, 120 × 120 × 0.2 at a pressure of 200 kgf / cm ^2.
mm test sheet was prepared. The characteristics of the samples obtained in the same manner were measured and the results are shown in Table 2.

[0024]

[Table 2]

The resin fine particles in Table 2 are as follows.・ Resin particles In a glass container of 5 liters, water with pH 6.8 3,660 g and concentration 28
90% by weight of ammonia water was charged and stirred. To the obtained mixed liquid, 750 g of methyltrimethoxysilane was added dropwise over 3 hours while maintaining the liquid temperature at 5 to 10 ° C. under low speed stirring with the rotation speed of the stirring blade being 200 rpm. Furthermore, the liquid temperature is 5
After stirring for 4 hours while keeping at ~ 10 ℃, keep the liquid temperature at 40-50 ℃.
And stirred at this temperature for 1 hour to obtain a silicone gel slurry. The silicone gel slurry was pressure filtered to form a cake with a water content of about 30% by weight, and
It was dried in a drier for 8 hours and crushed with a jet mill. The obtained fine particles were spherical particles having a particle size of 1.6 to 2.0 μm and containing silanol groups on the surface in an amount of about 0.0005 mol / 100 g. To a mixture of 100 parts of these spherical particles and 100 parts of toluene was added 2 parts of disilazane having an average composition formula of {(CH ₃ ) ₃ Si [OSi (CH ₃ ) ₂ ] ₃₀ } ₂ NH and reacted at 120 ° C for 6 hours. Let Subsequently, the toluene was distilled off under reduced pressure, the residue was washed with hexane, the powder was separated with a centrifuge, and the powder was dried at 80 ° C. for 2 hours to obtain resin fine particles whose surface was covered with a polydimethylsiloxanyl group.

[0026]

EFFECT OF THE INVENTION The thermoplastic resin composition of the present invention has a small dynamic friction coefficient, good sliding property, excellent blocking resistance, good water repellency and stain resistance, and has such characteristics. Since the conventional product does not have good transparency, it gives a molded product with good transparency, and thus it is superior to conventional products together with the molded product using this composition.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08L 83/07 C08L 83/07 // (C08L 101/00 83:04) (72) Inventor Yamamoto Akira 1 Hitomi, Oita, Matsuida-cho, Usui-gun, Gunma Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory

Claims (4)

[Claims] 1. A thermoplastic resin having 100 parts by weight and a surface of the general formula (I): (In the formula, R represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, 50 mol% or more of all R are methyl groups, and n represents an integer of 5 or more and 200 or less. ), The average particle size of the polysiloxanyl group bonded is 0.5 to 20 μm.
A thermoplastic resin composition obtained by uniformly dispersing 0.1 to 10 parts by weight of the spherical silicone resin fine particles. 2. The spherical silicone resin fine particles bonded with a polysiloxanyl group are spherical silicone resin fine particles containing CH ₂ = CHSiO _1.5 units, and a compound of the general formula (II): The thermoplastic resin composition according to claim 1, which is a hydrosilylation reaction product with a compound represented by the formula (wherein R and n are the same as in claim 1). 3. The spherical silicone resin fine particles to which the polysiloxanyl group is bonded are spherical silicone resin fine particles containing a silanol group, and a compound of the general formula (III): The thermoplastic resin composition according to claim 1, which is a reaction product with a compound represented by the formula (wherein R and n are the same as in claim 1). 4. A molded article produced from the thermoplastic resin composition according to claim 1.